Benzotriazole based UV absorbers and photographic elements containing them

ABSTRACT

An ultraviolet absorbing compound of formula (I) below, and photographic elements containing such a compound as an ultraviolet absorber: ##STR1## wherein: R 4  is H or an alkyl group, and the benzo or phenyl ring shown may be further substituted or unsubstituted; 
     X is --C(O)O-- wherein the carbonyl carbon is bonded to the N of NR 4 , or X is --SO 2  --; 
     L is a bivalent linking group; 
     p is 0 or 1; 
     A* is an alkyl group having an asymmetric carbon or silicon atom, and; 
     wherein the ultraviolet absorbing compound of formula (I) is a mixture of two enantiomers about the asymmetric carbon or silicon of A*.

FIELD OF THE INVENTION

This invention relates to particular benzotriazole based UV absorbingcompounds, and to photographic elements containing such compounds.

BACKGROUND

Typical photographic elements use silver halide emulsions, the silverhalide having a native sensitivity to ultraviolet radiation. Ultravioletradiation ("UV") as used in this application means light having awavelength of 300-400 nm. Such UV sensitivity is usually undesirable inthat it produces an image on the photographic element which is notvisible to the human eye. Furthermore, the image dyes in the colorphotographs are known to fade due to action of UV light. Also otherorganic molecules such as unused color forming couplers in the emulsionlayers and optical brighteners in the paper support degrade due toaction of UV light and generate undesirable color stains on the finishedphotographs. Therefore, photographic elements typically contain a UVabsorbing compound (sometimes referred to simply as a "UV absorber").Another function of UV absorbers is to prevent the formation ofundesirable patterns caused by electrostatic discharge in silver halidephotographic materials. In general, UV absorbers impart light stabilityto organic molecules in various products which are susceptible todegrade as a result of the action of UV.

Generally, an effective UV absorber should have its peak absorptionabove a wavelength of 320 nm. The absorption peak may be at a longerwavelength, as long as absorption drops off sufficiently as itapproaches the visual range (approximately 400 to 700 nm) so that novisible color is shown by the compound. In addition, to be effective, aUV absorber should have a high extinction coefficient in the desiredwavelength range. However, for the most desirable UV protection, thehigh extinction coefficient should be at those wavelengths sufficientlybelow the visual range so that the compound should not be visuallyyellow.

UV absorbers of the benzotriazole class for photographic and otherapplications are well known. They include hydroxyphenyl benzotriazoleswith various substituents on the hydroxyphenyl ring, including alkoxy.Compounds of the foregoing type are disclosed, for example, in Japanesepublished patent application JP 3139589. U.S. Pat. No. 5,112,728discloses photographic elements with liquid hydroxyphenyl benzotriazoleUV absorbers, including one example which incidentally has a racemiccarbon center. Also, U.S. Pat. Nos. 4,975,360; 4,973,701 and 4,996,326all disclose photographic elements which contain liquid hydroxyphenylbenzotriazoles as UV absorbers. U.S. Pat. Nos. 4,973,701 and 4,992,358discuss various advantages of the absorbers being liquid. Some of thecompounds in those patents include substituents on the hydroxyphenylring which incidentally have a racemic carbon center.

2-Hydroxyphenyl benzotriazole UV absorbers with a large class ofacylamino groups, including carbamates, sulfonamides, and many others,are described in FR 1,330,378, FR 1,324,898, FR 1,324,897, GB 991 204,GB 991 320, GB 991 142, GB 991 630, and GB 991 204. However, none of thecompounds disclosed in those references provide a carbamate with anasymmetric carbon.

UV absorbers which are currently used in photographic products includethose of formula (II-A) and (II-B) below: ##STR2## However, compounds(II-A) and (II-B) have a propensity to crystallize out during coldstorage of a dispersion of them.

It is therefore desirable to have other UV absorbing compounds suitablefor photographic uses, which are relatively stable in a photographicenvironment, and in particular have a low tendency to crystallize out atordinary temperatures at which photographic elements are used and/orstored, which have a high extinction coefficient so that less of itneeds to be used to obtain the same UV absorption, and which have a goodUV absorption spectrum for photographic uses.

SUMMARY OF THE INVENTION

The present invention provides ultraviolet absorbing compounds offormula (I) below, and photographic elements containing them: ##STR3##wherein: R₄ is H or an alkyl group, and the benzo or phenyl ring shownmay be further substituted or unsubstituted;

X is --C(O)O-- wherein the carbonyl carbon is bonded to the N of NR₄, orX is --SO₂ --;

L is a bivalent linking group;

p is 0 or 1;

A* is an alkyl group having an asymmetric carbon or silicon atom, and;

wherein the ultraviolet absorbing compound of formula (I) is a mixtureof two enantiomers about the asymmetric carbon or silicon of A*.

UV absorbing compounds of formula (I) have a wavelength of maximumabsorption ("λmax") which is desirable in the longer UV region (336-380nm), have a sharp dropping absorption profile at wavelengths slightlyshorter than 400 nm making them useful with known fluorescentbrighteners, are relatively stable in the environment of a photographicelement, do not readily crystallize in photographic elements, and havehigh extinction coefficients.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the normalized absorption spectra in methanolic solutionfor a mixture of comparative control compounds II-A and II-B (solidline), as well as for the inventive compound V (dotted line); and

FIG. 2 shows the absorption spectra of coatings in a photographicelement of inventive compound V and the comparative compounds II-A andII-B, in total transmission mode, as described below.

EMBODIMENTS OF THE INVENTION

In the present application, reference to ultraviolet or UV in relationto the present invention refers to the wavelength range of 300 to 400 nmunless the contrary is indicated. Additionally, reference to "under","above", "below", "upper", "lower" or the like terms in relation tolayer structure of a photographic element, is meant the relativeposition in relation to light when the element is exposed in a normalmanner. "Above" or "upper" would mean closer to the light source whenthe element is exposed normally, while "below" or "lower" would meanfurther from the light source. Since a typical photographic element hasthe various layers coated on a support, "above" or "upper" would meanfurther from the support, while "below" or "under" would mean closer tothe support. Further, reference to any chemical "group" (such as alkylgroup, aryl group, heteroaryl group, and the like) includes thepossibility of it being both substituted or unsubstituted (for example,alkyl group and aryl group include substituted and unsubstituted alkyland substituted and unsubstituted aryl, respectively). Generally, unlessotherwise specifically stated, substituent groups usable on moleculesherein include any groups, whether substituted or unsubstituted, whichdo not destroy properties necessary for the photographic utility. Itwill also be understood throughout this application that reference to acompound of a particular general formula includes those compounds ofother more specific formula which specific formula falls within thegeneral formula definition.

As is well known, enantiomers have identical structural formulas exceptthey are non-superimposable mirror images of one another. Further, inreference to enantiomeric mixtures, proportions are in mole ratios. Whenreference is made in this application to the ultraviolet absorbingcompound of formula (I) being a mixture of two enantiomers about theasymmetric carbon or silicon of A*, this refers to a mixture of the twooptical isomers about the racemic carbon or silicon of A* with R and Sstereochemical configurations.

In compounds of formula (I), the bivalent linking group L may, forexample, be an alkylene group having a chain of 2 to 20 atoms in length,with or without intervening oxygen, sulfur or nitrogen atoms. However,preferably the carbon atoms of L are all saturated. This means that noneof the carbon atoms of L would have any type of carbon-carbon double ortriple bonds. Thus, in this situation L would not have groups such as--C═C-- or --C.tbd.C--. The possibility of L having unsaturated atomsother than unsaturated carbon atoms, is not excluded. For example, Lcould be a group such as (A) below: ##STR4##

More particularly, L may have from 1 to 20 carbon atoms (or 1 to 10, 1to 6, or 1 to 3 carbon atoms). L may particularly be an alkylene group.L may be unsubstituted or substituted with, for example, a 1 to 10carbon alkoxy (or 1 to 6, or 1 to 2 carbon alkoxy), a 1 to 10 carbonatom alkyl sulfide (or 1 to 6, or 1 to 2 carbon alkyl sulfide), 0 to 10carbon amino (or 0 to 6, or 0 to 2 carbon amino), or halogen. As alreadydescribed, L may contain intervening oxygen, sulfur or nitrogen atoms,such as 1 to 5 atoms of any of the foregoing type (or 1 or 2 interveningatoms selected from oxygen, sulfur or nitrogen atoms). By L beingsubstituted includes the possibility of the substituents forming a ring.For example, L could then include an alicyclic or heterocylic ring (suchas a 3 to 10 or 4, 5, or 6, membered ring). When the ring isheterocyclic it may contain, for example, have 1, 2, or 3 heteroatoms(which may be the same or different) selected from 0, S or N. Examplesof such rings as part of L include cyclohexyl, pyrrolidinyl,tetrahydrofuranyl, tetrahydrothienyl or piperidinyl, although lesspreferably such rings could also include benzo, pyrrolo, furyl, thienyl,pyridyl or spiro-ether containing rings. L may include as a substituent,particularly when L is an alkylene group as described (that is with orwithout the intervening heteroatoms described), an ether or estercontaining group. Particularly, the ether or ester containingsubstituent in L may be of the formula R₈ --O--(R₉)_(n) -- or R₈C(O)--(R₉)_(n) ⁻, where R₈ and R₉ are, independently, an alkyl group andn is 0 or 1. R₉ may have, for example, 1 to 6 carbon atoms, while R₈ mayhave, for example, 1 to 20 carbon atoms (for example, 1 to 10, or 6 to10).

The benzo ring and the hydroxy substituted phenyl ring may each befurther substituted. For example, either may have 1 to 4 furthersubstituents. Substituents may, for example, independently be, 1 to 18carbon alkyl (or 1 to 6, or 1 to 2 carbon alkyl), aryl (such as 6 to 20carbon atoms), heteroaryl (such as pyrrolo, furyl or thienyl), aryloxy(such as 6 to 20 carbon atoms) alkoxy (such as 1 to 6 or 1 to 2 carbonalkoxy), cyano, or halogen (for example F or Cl, particularly having Clon the benzo ring at the 5 and/or 6 position, and/or on the hydroxysubstituted phenyl at the 5' positon). Substituents for the benzo ringcan also include ring fused thereto, such as a benzo, pyrrolo, furyl orthienyl ring. Any of the alkyl and alkoxy substituents may have from 1to 5 (or 1 to 2) intervening oxygen, sulfur or nitrogen atoms, includingor not including asymmetric centers.

R₄ is preferably H. However, when R₄ is an alkyl group, it may have, forexample, from 1 to 20 C atoms (or 1 to 10 or 1 to 6 carbon atoms, suchas methyl, ethyl, primary or secondary propyl, or butyl or pentyl eitherof which may be normal, secondary or tertiary). Substituents includealkoxy (particularly 1 to 6 carbon atoms), halogen (particularly Cl andF), and cyano. When R₄ is an alkyl group though, it is preferably anelectron withdrawing alkyl group.

When R₄ is not an electron withdrawing alkyl group, there may be ahypsochromic shift (shift to a shorter wavelength) in the wavelenght ofmaximum UV absorption of a formula (I) compound, as well as a lowermolar extinction coefficient (versus the case when R₄ is H). If desired,in such case the wavelength of maximum UV absorption may be againshifted longer by providing a substituent for R₁ or R₂ on the benzo ringof the benzotriazole, which has an unshared electron pair. Suchsubstituents include Cl, F, dialkylamino, or an alkoxy.

Electron withdrawing substituents in general, these are discussed inMarch, Advanced Organic Chemistry, 3rd Ed., J. March, (John Wiley Sons,NY; 1985) at pages 20-21, 228-229, 386-387, 494-497. In particular,preferred electron withdrawing substituents in each case describedherein, or an electron withdrawing alkyl group for R₄, would have aHammett σ_(p) constant of greater than 0 (or greater than 0.1 or even0.3) and preferably between 0.1 to 1.0 (for example, between any of 0.3,0.4, 0.5 or 0.6 to 1.0). Hammett σ_(p) values are discussed in theforegoing Advanced Organic Chemistry. Note that the "p" subscript refersto the fact that the σ values are measured with the substituents in thepara position of a benzene ring. Additional tables relating to Hammettσ_(p) constants can be found in Chemical Reviews Volume 91, pages165-195 (authored by C. Hansch et al.).

As for A*, any alkyl group with an asymmetric carbon atom could be used.With the appropriate substituents on the asymmetric carbon, A* may haveas little as only 1 carbon atom. Examples of A* could include However,the asymmetric carbon atom will preferably have at least three differentalkyl groups, which means that A* will therefore preferably have atleast 4 carbon atoms. A* may have 1 to 20 C atoms (or preferably 4 to 20C atoms, 4 to 10 or 4 to 6 carbon atoms). A* is preferably of thestructure --CR₅ R₆ R₇ as shown below in structure (Ia).

The compounds of formula (I) may particularly be of formula (Ia) below(some of carbon atoms on the rings being numbered in formula (Ia) toillustrate how the positions on the rings of benzotriazoles areidentified in this application): ##STR5## or more particularly offormula (Ib): ##STR6##

More particularly, in any of the above formula (I) or, (Ia), or (Ib),R₁, R₂ and R₃ may be, independently, 1 to 18 (or 1 to 10, 1 to 6, or 1to 2) carbon alkyl or alkoxy either of which may have 1-5 (or 1 or 2)intervening oxygen, sulfur or nitrogen atoms, or are aryl, heteroaryl,or aryloxy. R₃ may also be a 6'-hydroxy substituent. R₁, R₂ and R₃ mayalso be, independently any of the foregoing substituted with 1 to 17 (or1 to 10, 1 to 6, or 1 or 2) carbon alkoxy, 1 to 17 (or 1 to 10, 1 to 6,or 1 or 2) carbon alkyl sulfide, 0 to 17 carbon amino (or 0 to 10, 0 to6, or 0 to 2), or a halogen, or any of R₁, R₂ or R₃ may be H or ahalogen (particularly chloro or fluoro) or both R₁ and R₂ together forma 5 to 18 carbon atom aryl group (such as a benzo ring) or heteroarylring group (for example, pyrrolo, furyl, thienyl, pyridyl). Substituentson the foregoing rings formed by R₁ and R₂ may include a 1 to 17 (or 1to 10, 1 to 6, or 1 or 2) carbon atom alkyl or alkoxy, or a halogen.

R₁, R₂ and R₃ may also be, independently: a chloro; a fluoro; a hydroxy;a cyano; a carboxy; a carbalkoxy; a nitro; an acylamino group (forexample, an acetylamino group), carbamoyl, sulfonyl, sulfamoyl,sulfonamido, acyloxy (for example, an acetoxy group or a benzoyloxygroup), or an oxycarbonyl group (for example, a methoxycarbonyl group,etc.), any of which may have 1 to 18 (or 1 to 10, 1 to 6, or 1 to 2)carbon atoms.

Also, L may particularly have a total of 1 to 20 (or 1 to 10, or 1 to 4)atoms and be an alkylene group of which may have 1-5 (or 1, 2 or 3)intervening oxygen, sulfur or nitrogen atoms. Substituents on L include,for example, a 1 to 10 (or 1 to 6, or 1 or 2) carbon alkoxy, a 1 to 10(or 1 to 6, or 1 or 2) carbon atom alkyl sulfide, 0 to 10 (or 0 to 6, or0 to 2) carbon amino, or with halogen. L may particularly be anunsubstituted methine (that is, only one carbon atoms in length with nointervening heteroatoms) or a methine substituted with 1 to 12 (or 1, 2or 3) carbon atom alkyl or alkoxy (either with or without 1 or 2intervening oxygen atoms), or with a 0 to 6 (or 0, 1, 2, or 3) carbonatom amino, or a halogen (such as F or Cl).

In the above formulas, R₅, R₆ and R₇ are, independently: H; halogen;cyano; an alkyl group or alkoxy group; thioalkyl group; alkylamino orarylamino group; an aryl group or aryloxy group; or a heteroaryl group.When any of R₅, R₆ and R₇ is an alkyl or alkoxy group it may, forexample, have from 1 to 20 C atoms (or 1 to 10 or 1 to 6, such asmethyl, ethyl, propyl, butyl or pentyl). Suitable aryl groups, aryloxygroups or heteroaryl groups may be selected from such groups asdescribed in connection with R₁, R₂ and R₃ above. Substituents on any ofthe foregoing groups for R₅, R₆ and R₇ may be selected from among thesubstituents on corresponding groups for R₁, R₂ and R₃ described above.Such substituents include alkoxy (particularly 1 to 6 carbon atoms),halogen (particularly Cl and F), and cyano. It is preferred that each ofR₅ , R₆ and R₇ is selected from H or alkyl groups.

It is important for the present invention that R₅, R₆ and R₇ bedifferent such that the carbon or silicon atom bearing those groups isasymmetric (a racemic carbon or silicon center). However, the compoundof formula (I) could have further racemic carbon centers. When R₁, R₂,R₃ or R₄ also contains an asymetric carbon (or any other substituentalso contains an asymmetric carbon), such that there are two or moreasymmetric carbons in the compound, diastereomers can then be formed.This means that the UV absorbing compound of formula (I) could then havemore than one pair of enantiomers. However, the compound shouldpreferably have a 60/40 to 40/60 (preferably 50/50) ratio of at leasttwo enantiomers (although it can have, for example a 60/40 to 40/60ratio of enantiomers in each of two sets of enantiomers).

It should be noted that UV absorbing compounds are specificallycontemplated which are of formula (I) (including formula (Ia), (Ib) andall the specific examples below) but in which the entire linkage of--N--X--(L)_(p) --A* is on the 5- or 6- position of the benzene ring ofthe benzotriazole. In such cases, the 4'-position of the hydroxyphenylring could be substituted with any of those substituents described abovefor R₁ or R₂. However, while such compounds are specificallycontemplated, they are not considered compounds of the present invention(which require the --N--X--(L)_(p) --A* to be in the 4'-position asshown in formula (I).

Examples of compounds of the present invention are shown below. Furthercompounds of formula (I) are described in the Examples below. ##STR7##

                                      TABLE A                                     __________________________________________________________________________    # R.sub.1                                                                            R.sub.2                                                                              R.sub.3                                                                           R.sub.4  L                R.sub.5                                                                          R.sub.6                                                                          R.sub.7                     __________________________________________________________________________    1 H    5-F    H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             2 H    5-Cl   H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             3 H    5-F    H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             4 H    H      H   CH.sub.2 COOCH.sub.3                                                                   CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             5 H    H      H   CF.sub.2 COOCF.sub.3                                                                   CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             6 H    H      H   CF.sub.2 CF.sub.3                                                                      CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             7 H    H      H   H        (CH.sub.2).sub.2 CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             8 H    H      6'-OH                                                                             H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             9 H    H      6'-OH                                                                             C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             10                                                                              H    H      6'-OH                                                                             CH.sub.3 CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             11                                                                              6-CH.sub.3 O                                                                       5-CH.sub.3 O                                                                         H   C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             12                                                                              H    5-CH.sub.3 O                                                                         H   C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             13                                                                              H    5-Cl   H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             14                                                                              H    5-sec-C.sub.4 H.sub.9 O                                                              H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             15                                                                              H    5-CH.sub.3 O                                                                         H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             16                                                                              H    H      5'-Cl                                                                             sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             17                                                                              H    H      5'-Cl                                                                             sec-Butyl                                                                              CH.sub.2         H  CH.sub.3                                                                         C.sub.2 H.sub.5             18                                                                              H    H      5'-F                                                                              sec-Butyl                                                                              CH.sub.2         H  CH.sub.3                                                                         C.sub.2 H.sub.5             19                                                                              6-F  5-F    H   CH.sub.2 SO.sub.2 O-s-C.sub.4 H.sub.9                                                  CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             20                                                                              H    5-s-C.sub.4 H.sub.9 S                                                                H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             21                                                                              H    5-s-(C.sub.4 H.sub.9)N                                                               H   Ethyl    CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             22                                                                              H    H      H   H        CH.sub.2 OCH.sub.2 CH.sub.2 O                                                                  H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             23                                                                              H    H      H   H        (CH.sub.2 OCH.sub.2 CH.sub.2 O).sub.2                                                          H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             24                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2                                                                           H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             25                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2                                                                           H  CH.sub.3                                                                         C.sub.4 H.sub.9             26                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                   H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             27                                                                              H    H      H   H                                                                                                       H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             28                                                                              H    H      H   H                                                                                       ##STR8##        H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             29                                                                              H    H      H   H                                                                                       ##STR9##        H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             __________________________________________________________________________     ##STR10##

                                      TABLE B                                     __________________________________________________________________________    # R.sub.1                                                                            R.sub.2                                                                              R.sub.3                                                                           R.sub.4  L                R.sub.5                                                                          R.sub.6                                                                          R.sub.7                     __________________________________________________________________________    1 H    5-F    H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             2 H    5-Cl   H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             3 H    5-F    H   H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             4 H    H      H   CH.sub.2 COOCH.sub.3                                                                   CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             5 H    H      H   CF.sub.2 COOCF.sub.3                                                                   CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             6 H    H      H   CF.sub.2 CF.sub.3                                                                      CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             7 H    H      H   H        (CH.sub.2).sub.2 CH.sub.3                                                                         C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             8 H    H      6'-OH                                                                             H        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             9 H    H      6'-OH                                                                             C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             10                                                                              H    H      6'-OH                                                                             CH.sub.3 CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             11                                                                              6-CH.sub.3 O                                                                       5-CH.sub.3 O                                                                         H   C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             12                                                                              H    5-CH.sub.3 O                                                                         H   C.sub.2 H.sub.5                                                                        CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             13                                                                              H    5-Cl   H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             14                                                                              H    5-sec-C.sub.4 H.sub.9 O                                                              H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             15                                                                              H    5-CH.sub.3 O                                                                         H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             16                                                                              H    H      5'-Cl                                                                             sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             17                                                                              H    H      5'-Cl                                                                             sec-Butyl                                                                              CH.sub.2         H  CH.sub.3                                                                         C.sub.2 H.sub.5             18                                                                              H    H      5'-F                                                                              sec-Butyl                                                                              CH.sub.2         H  CH.sub.3                                                                         C.sub.2 H.sub.5             19                                                                              6-F  5-F    H   CH.sub.2 SO.sub.2 O-s-C.sub.4 H.sub.9                                                  CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             20                                                                              H    5-s-C.sub.4 H.sub.9 S                                                                H   sec-Butyl                                                                              CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             21                                                                              H    5-s-(C.sub.4 H.sub.9)N                                                               H   Ethyl    CH.sub.2         H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             22                                                                              H    H      H   H        CH.sub.2 OCH.sub.2 CH.sub.2 O                                                                  H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             23                                                                              H    H      H   H        (CH.sub.2 OCH.sub.2 CH.sub.2 O).sub.2                                                          H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             24                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2                                                                           H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             25                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2                                                                           H  CH.sub.3                                                                         C.sub.4 H.sub.9             26                                                                              H    H      H   H        CH.sub.2 COOCH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                   H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             27                                                                              H    H      H   H                                                                                                       H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             28                                                                              H    H      H   H                                                                                       ##STR11##       H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9             29                                                                              H    H      H   H                                                                                       ##STR12##       H  C.sub.2 H.sub.5                                                                  C.sub.4 H.sub.9              ##STR13##                                                                    Compound 30 of Table B                                                        __________________________________________________________________________     # is the Compound number                                                 

UV absorbing compounds of formula (I) can be prepared from thechromophore of formula (III), below. The compounds of formula (III) canbe readily synthesized from inexpensively available starting materialssuch as o-nitroaniline, 4-chloro-2-nitroaniline and m-amino orm-aminoalkyl substituted phenols by procedures known in the art (See,for example, U.S. Pat. No. 3,813,255). For example, the2-(2'-hydroxy-4'-aminophenyl)benzotriazole can be made by reacting2-nitrobenzenediazonium chloride with 3-aminophenol followed byreductive ring closure of the azo dye to the desired benzotriazole.Details of the synthesis of compounds of formula (I) are describedbelow. Further compounds of formula (I) can be prepared in an analogousmanner. It will be understood in each example below, that one of thestarting reagents (for example, the alkoxycarbonyl chloride) is thecorresponding enantiomeric mixture (preferably, a 40/60 to 60/40enantiomeric mixture). ##STR14##

The carbamate containing UV compounds of the present invention couldalternatively be synthesized by condensing the amino-substitutedbenzotriazole compounds with the corresponding alcohol counterpart inpresence of Di-2-pyridyl carbonate ("DPC") (structure (IV) shown below)as a condensing agent in the presence of an inert solvent such as ethylacetate or tetrahydrofuran. This chemistry may eliminate the use ofoxycarbonyl chlorides which require a great deal of caution in theirhandling. ##STR15##

The following method is the preferred mode of synthesis. In the detailedexamples below, syntheses of inventive compound (V) and its analogs wereperformed by the Scheme 1 shown below. Scheme 1 describes the preferredmode of synthesizing the inventive compound (V) eliminating the use oforganic base N,N-dimethylaniline (a reagent which is difficult to removeduring purification/or work-up), instead using potassium bicarbonate (avery mild inorganic base, easily removable due to its high solubility inwater). This synthesis by the preferred mode was first described on amodel compound, such as condensing m-amino phenol with methoxycarbonylchloride to generate exclusively a carbamate linkage, in the known art(See, for example, V. F. Pozdnev, Khimiya GeterotsiklicheskikhSoedinenii, No. 3, 312-314 (1990)). However, this procedure has not beendescribed before with any appropriately substituted benzotriazolecompounds of this invention. ##STR16##

Photographic elements according to the present invention will typicallyhave at least one light sensitive silver halide emulsion layer and anon-light sensitive layer, with the ultraviolet absorbing compound offormula (I) being typically (but not necessarily) located in thenon-light sensitive layer. More preferably, a photographic element ofthe present invention will have the non-light sensitive layer containingthe ultraviolet absorbing compound located above all light sensitivelayers. However, it is also contemplated that the ultraviolet absorbingcompound can additionally be present in another layer, such as aninterlayer (or even a light sensitive layer), particularly an interlayerlocated between red and green sensitive layers in an element havingblue, green and red-sensitive layers coated in that order, on a support(particularly a paper support). Any layer of the photographic element inwhich the UV absorbing compounds of formula (I) are located willnormally be a gel layer, and the UV absorbing compound may particularlybe dispersed therein using a coupler solvent with or without additionalethyl acetate.

The UV absorbing compounds can be directly dispersed in the element ordispersed therein in droplets of a solvent dispersion. Alternatively,the UV absorbing compounds of formula (I) can be loaded into a polymerlatex by themselves or with other compounds such as high boiling pointorganic solvents or monomeric UV absorbing compounds. "Loading" apolymer latex is generally described in U.S. Pat. No. 4,199,363 forexample. Loading of a polymer latex is also described, for example, inU.S. Pat. Nos. 4,203,716, 4,214,047, 4,247,627, 4,497,929 and 4,608,424.

As described, UV absorbing compounds of the present invention arepreferably used by themselves in a photographic element. However, theymay be used in conjunction with other UV absorbing compounds if desired,such as other benzotriazole based UV absorbers. Examples of suchconventional UV absorbing agents which can be used include:2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chloro-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di(1,1-dimethylbenzyl)-phenyl)-2H-benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole. Other types of UVabsorbing agents such as p-hydroxybenzoates, phenylesters of benzoicacid, salicylanilides and oxanilides, diketones, benzylidene malonate,esters of α-cyano-cinnamic acid, and organic metal photostabilizers, andothers, as described in J. F. Rabek, Photostabilization of Polymers,Principles and Applications, Elsevier Science Publishers LTD, England,page 202-278(1990).

The UV absorbing compound is incorporated into the photographic element(typically into a gelatin gel thereof) in an amount of between 0.2 g/m²to 10 g/m², and more preferably between 0.5 g/m² to 5.0 g/m².Furthermore, when incorporated as a solvent dispersion using a waterimmiscible organic solvent, the weight ratio of high boiling, waterimmiscible organic solvent to UV absorbing compound is preferablybetween 0.1 to 5.0 (that is, 0.1/1 to 5.0/1 of solvent/UV absorbingcompound), and more preferably between 0.2 to 3.0 (that is, 0.2/1 to3.0/1 of solvent/UV absorbing compound).

The UV absorbing compound of formula (I) is provided in any one or moreof the layers (for example, a hydrophilic colloid layer such as agelatin layer) of a photographic light-sensitive material (for example,a silver halide photographic light-sensitive material), such as asurface protective layer, an intermediate layer or a silver halideemulsion layer, and the like. For example, in photographic paper the UVabsorbing compound of formula (I) with/without other UV absorbingcompounds, may be positioned above and/or below the red sensitive layer(typically adjacent to it), the red sensitive layer typically being theuppermost light sensitive layer in color paper, or even completely orpartially within the red sensitive layer. The UV absorbing compound istypically provided in a given layer of a photographic element by coatingthe hydrophilic colloid material (such as a gelatin emulsion) whichcontains the latex, onto a support or another previously coated layerforming part of the element.

The photographic elements made by the method of the present inventioncan be single color elements or multicolor elements. Multicolor elementscontain dye image-forming units sensitive to each of the three primaryregions of the spectrum. Each unit can be comprised of a single emulsionlayer or of multiple emulsion layers sensitive to a given region of thespectrum. The layers of the element, including the layers of theimage-forming units, can be arranged in various orders as known in theart. In an alternative format, the emulsions sensitive to each of thethree primary regions of the spectrum can be disposed as a singlesegmented layer.

A typical multicolor photographic element comprises a support bearing acyan dye image-forming unit comprised of at least one red-sensitivesilver halide emulsion layer having associated therewith at least onecyan dye-forming coupler, a magenta dye image-forming unit comprising atleast one green-sensitive silver halide emulsion layer having associatedtherewith at least one magenta dye-forming coupler, and a yellow dyeimage-forming unit comprising at least one blue-sensitive silver halideemulsion layer having associated therewith at least one yellowdye-forming coupler. The element can contain additional layers, such asfilter layers, interlayers, overcoat layers, subbing layers, and thelike. All of these can be coated on a support which can be transparentor reflective (for example, a paper support). Photographic elements ofthe present invention may also usefully include a magnetic recordingmaterial as described in Research Disclosure, Item 34390, November 1992,or a transparent magnetic recording layer such as a layer containingmagnetic particles on the underside of a transparent support as in U.S.Pat. Nos. 4,279,945 and 4,302,523. The element typically will have atotal thickness (excluding the support) of from 5 to 30 microns. Whilethe order of the color sensitive layers can be varied, they willnormally be red-sensitive, green-sensitive and blue-sensitive, in thatorder on a transparent support, (that is, blue sensitive furthest fromthe support) and the reverse order on a reflective support beingtypical.

The present invention also contemplates the use of photographic elementsof the present invention in what are often referred to as single usecameras (or "film with lens" units). These cameras are sold with filmpreloaded in them and the entire camera is returned to a processor withthe exposed film remaining inside the camera. Such cameras may haveglass or plastic lenses through which the photographic element isexposed.

In the following discussion of suitable materials for use in elements ofthis invention, reference will be made to Research Disclosure, September1994, Number 365, Item 36544, which will be identified hereafter by theterm "Research Disclosure I." The Sections hereafter referred to areSections of the Research Disclosure I unless otherwise indicated. AllResearch Disclosures referenced herein are published by Kenneth MasonPublications, Ltd., Dudley Annex, 12a North Street, Emsworth, HampshireP010 7DQ, ENGLAND,

The silver halide emulsions employed in the elements of this inventioncan be either negative-working, such as surface-sensitive emulsions orunfogged internal latent image forming emulsions, or direct positiveemulsions of the unfogged, internal latent image forming type which arepositive working when development is conducted with uniform lightexposure or in the presence of a nucleating agent. Suitable emulsionsand their preparation as well as methods of chemical and spectralsensitization are described in Sections I through V. Color materials anddevelopment modifiers are described in Sections V through XX. Vehicleswhich can be used in the elements of the present invention are describedin Section II, and various additives such as brighteners, antifoggants,stabilizers, light absorbing and scattering materials, hardeners,coating aids, plasticizers, lubricants and matting agents are described,for example, in Sections VI through X and XI through XIV. Manufacturingmethods are described in all of the sections, other layers and supportsin Sections XI and XIV, processing methods and agents in Sections XIXand XX, and exposure alternatives in Section XVI.

With negative working silver halide a negative image can be formed.Optionally a positive (or reversal) image can be formed although anegative image is typically first formed.

The photographic elements of the present invention may also use coloredcouplers (for example to adjust levels of interlayer correction) andmasking couplers such as those described in EP 213 490; JapanesePublished Application 58-172,647; U.S. Pat. No. 2,983,608; GermanApplication DE 2,706,117C; U.K. Patent 1,530,272; Japanese ApplicationA-113935; U.S. Pat. No. 4,070,191 and German Application DE 2,643,965.The masking couplers may be shifted or blocked.

The photographic elements may also contain materials that accelerate orotherwise modify the processing steps of bleaching or fixing to improvethe quality of the image. Bleach accelerators described in EP 193 389;EP 301 477; U.S. Pat. Nos. 4,163,669; 4,865,956; and 4,923,784 areparticularly useful. Also contemplated is the use of nucleating agents,development accelerators or their precursors (UK Patent 2,097,140; U.K.Patent 2,131,188); electron transfer agents (U.S. Pat. Nos. 4,859,578;4,912,025); antifogging and anti color-mixing agents such as derivativesof hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbicacid; hydrazides; sulfonamidophenols; and non color-forming couplers.

The elements may also contain filter dye layers comprising colloidalsilver sol or yellow and/or magenta filter dyes and/or antihalation dyes(particularly in an undercoat beneath all light sensitive layers or inthe side of the support opposite that on which all light sensitivelayers are located) either as oil-in-water dispersions, latexdispersions or as solid particle dispersions. Additionally, they may beused with "smearing" couplers (for example as described in U.S. Pat. No.4,366,237; EP 096 570; U.S. Pat. Nos. 4,420,556; and 4,543,323.) Also,the couplers may be blocked or coated in protected form as described,for example, in Japanese Application 61/258,249 or U.S. Pat. No.5,019,492.

The photographic elements may further contain other image-modifyingcompounds such as "Developer Inhibitor-Releasing" compounds (DIR's).Useful additional DIR's for elements of the present invention, are knownin the art and examples are described in U.S. Pat. Nos. 3,137,578;3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506;3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984;4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437;4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634;4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601;4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179;4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835;4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662;GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE3,644,416 as well as the following European Patent Publications:272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346;373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.

DIR compounds are also disclosed in "Developer-Inhibitor-Releasing (DIR)Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P. W.Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969),incorporated herein by reference.

It is also contemplated that the concepts of the present invention maybe employed to obtain reflection color prints as described in ResearchDisclosure, November 1979, Item 18716, available from Kenneth MasonPublications, Ltd, Dudley Annex, 12a North Street, Emsworth, HampshireP0101 7DQ, England, incorporated herein by reference. This reference andall other references cited in this application are incorporated hereinby reference.

The emulsions and materials to form elements of the present invention,may be coated on pH adjusted support as described in U.S. Pat. No.4,917,994; with epoxy solvents (EP 0 164 961); with additionalstabilizers (as described, for example, in U.S. Pat. Nos. 4,346,165;4,540,653 and 4,906,559); with ballasted chelating agents such as thosein U.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalent cationssuch as calcium; and with stain reducing compounds such as described inU.S. Pat. Nos. 5,068,171 and 5,096,805. Other compounds useful in theelements of the invention are disclosed in Japanese PublishedApplications 83-09,959; 83-62,586; 90-072,629, 90-072,630; 90-072,632;90-072,633; 90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336;90-079,338; 90-079,690; 90-079,691; 90-080,487; 90-080,489; 90-080,490;90-080,491; 90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670;90-087,361; 90-087,362; 90-087,363; 90-087,364; 90-088,096; 90-088,097;90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668;90-094,055; 90-094,056; 90-101,937; 90-103,409; 90-151,577.

The silver halide used in the photographic elements may be silveriodobromide, silver bromide, silver chloride, silver chlorobromide,silver chloroiodobromide, and the like. For example, the silver halideused in the photographic elements of the present invention may containat least 90% silver chloride or more (for example, at least 95%, 98%,99% or 100% silver chloride). In the case of such high chloride silverhalide emulsions, some silver bromide may be present but typicallysubstantially no silver iodide. Substantially no silver iodide means theiodide concentration would be no more than 1%, and preferably less than0.5 or 0.1%. In particular, in such a case the possibility is alsocontemplated that the silver chloride could be treated with a bromidesource to increase its sensitivity, although the bulk concentration ofbromide in the resulting emulsion will typically be no more than about 2to 2.5% and preferably between about 0.6 to 1.2% (the remainder beingsilver chloride). The foregoing % figures are mole %.

The type of silver halide grains preferably include polymorphic, cubic,and octahedral. The grain size of the silver halide may have anydistribution known to be useful in photographic compositions, and may beether polydipersed or monodispersed.

Tabular grain silver halide emulsions may also be used. Tabular grainsare those with two parallel major faces each clearly larger than anyremaining grain face and tabular grain emulsions are those in which thetabular grains account for at least 30 percent, more typically at least50 percent, preferably >70 percent and optimally >90 percent of totalgrain projected area. The tabular grains can account for substantiallyall (>97 percent) of total grain projected area. The tabular grainemulsions can be high aspect ratio tabular grain emulsions-that is,ECD/t >8, where ECD is the diameter of a circle having an area equal tograin projected area and t is tabular grain thickness; intermediateaspect ratio tabular grain emulsions--that is, ECD/t=5 to 8; or lowaspect ratio tabular grain emulsions-that is, ECD/t=2 to 5. Theemulsions typically exhibit high tabularity (T), where T (that is,ECD/t²) >25 and ECD and t are both measured in micrometers (μm). Thetabular grains can be of any thickness compatible with achieving an aimaverage aspect ratio and/or average tabularity of the tabular grainemulsion. Preferably the tabular grains satisfying projected arearequirements are those having thicknesses of <0.3 μm, thin (<0.2 μm)tabular grains being specifically preferred and ultrathin (<0.07 μm)tabular grains being contemplated for maximum tabular grain performanceenhancements. When the native blue absorption of iodohalide tabulargrains is relied upon for blue speed, thicker tabular grains, typicallyup to 0.5 μm in thickness, are contemplated.

High iodide tabular grain emulsions are illustrated by House U.S. Pat.No. 4,490,458, Maskasky U.S. Pat. No. 4,459,353 and Yagi et al EPO 0 410410.

Tabular grains formed of silver halide(s) that form a face centeredcubic (rock salt type) crystal lattice structure can have either {100}or {111} major faces. Emulsions containing {111} major face tabulargrains, including those with controlled grain dispersities, halidedistributions, twin plane spacing, edge structures and graindislocations as well as adsorbed {111} grain face stabilizers, areillustrated in those references cited in Research Disclosure I, SectionI.B.(3) (page 503).

The silver halide grains to be used in the invention may be preparedaccording to methods known in the art, such as those described inResearch Disclosure I and James, The Theory of the Photographic Process.These include methods such as ammoniacal emulsion making, neutral oracidic emulsion making, and others known in the art. These methodsgenerally involve mixing a water soluble silver salt with a watersoluble halide salt in the presence of a protective colloid, andcontrolling the temperature, pAg, pH values, etc, at suitable valuesduring formation of the silver halide by precipitation.

The silver halide to be used in the invention may be advantageouslysubjected to chemical sensitization with noble metal (for example, gold)sensitizers, middle chalcogen (for example, sulfur) sensitizers,reduction sensitizers and others known in the art. Compounds andtechniques useful for chemical sensitization of silver halide are knownin the art and described in Research Disclosure I and the referencescited therein.

The photographic elements of the present invention, as is typical,provide the silver halide in the form of an emulsion. Photographicemulsions generally include a vehicle for coating the emulsion as alayer of a photographic element. Useful vehicles include both naturallyoccurring substances such as proteins, protein derivatives, cellulosederivatives (for example, cellulose esters), gelatin (for example,alkali-treated gelatin such as cattle bone or hide gelatin, or acidtreated gelatin such as pigskin gelatin), gelatin derivatives (forexample, acetylated gelatin, phthalated gelatin, and the like), andothers as described in Research Disclosure I. Also useful as vehicles orvehicle extenders are hydrophilic water-permeable colloids. Theseinclude synthetic polymeric peptizers, carriers, and/or binders such aspoly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinylacetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates,hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine,methacrylamide copolymers, and the like, as described in ResearchDisclosure I. The vehicle can be present in the emulsion in any amountuseful in photographic emulsions. The emulsion can also include any ofthe addenda known to be useful in photographic emulsions. These includechemical sensitizers, such as active gelatin, sulfur, selenium,tellurium, gold, platinum, palladium, iridium, osmium, rhenium, rhodium,ruthenium, phosphorous, or combinations thereof. Chemical sensitizationis generally carried out at pAg levels of from 5 to 10, pH levels offrom 5 to 8, and temperatures of from 30° to 80° C., as illustrated inResearch Disclosure, June 1975, item 13452 and U.S. Pat. No. 3,772,031.

The silver halide may be sensitized by sensitizing dyes by any methodknown in the art, such as described in Research Disclosure I. The dyemay be added to an emulsion of the silver halide grains and ahydrophilic colloid at any time prior to (for example, during or afterchemical sensitization) or simultaneous with the coating of the emulsionon a photographic element. The dye/silver halide emulsion may be mixedwith a dispersion of color image-forming coupler immediately beforecoating or in advance of coating (for example, 2 hours).

Photographic elements of the present invention are preferably imagewiseexposed using any of the known techniques, including those described inResearch Disclosure I, section XVI. This typically involves exposure tolight in the visible region of the spectrum, and typically such exposureis of a live image through a lens, although exposure can also beexposure to a stored image (such as a computer stored image) by means oflight emitting devices (such as light emitting diodes, CRT and thelike).

Photographic elements comprising the composition of the invention can beprocessed in any of a number of well-known photographic processesutilizing any of a number of well-known processing compositions,described, for example, in Research Disclosure I, or in T. H. James,editor, The Theory of the Photographic Process, 4th Edition, Macmillan,New York, 1977. In the case of processing a reversal color element, theelement is first treated with a black and white developer followed bytreatment with a color developer to produce a positive dye image. In thecase of processing a negative color element, the first developer is acolor developer so as to produce a negative dye image. Preferred colordeveloping agents are p-phenylenediamines. Especially preferred are:

4-amino N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N,N-diethylaniline hydrochloride,

4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido) ethylanilinesesquisulfate hydrate,

4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate,

4-amino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochlorideand

4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonicacid.

Development is followed by bleach-fixing, to remove silver or silverhalide, washing and drying.

The present invention will be further described in the examples below.

The following specific examples illustrate the various aspects of thisinvention but are not intended to limit its scope.

EXAMPLE 1 Inventive Compound No. V

A 5.0-g (0,026 mole, 5.1 mL) sample of 2-ethylhexyloxycarbonyl chloridewas added dropwise during 30 minutes with mechanical stirring andcooling (10°-15° C.) to a suspension of 5.65 g (0,025 mole) of2-(2-hydroxy-4-amino phenyl)benzotriazole and 3.12 g (0.031 mole) ofKHCO₃ in 150 mL of ethyl acetate and 10 mL of water, after which themixture was stirred for another 3 hour. The aqueous layer was separated,and the organic layer was washed successively with water (100 mL), 1Msulfuric acid (20 mL), water (100 mL), brine (100 mL), dried (Na₂ SO₄),filtered, solvent was removed on rotary evaporator. Nearly colorlessviscous material was obtained which was diluted with 300 mL cold water.When this was triturated with a spatula, white solid was obtained. Thiswas filtered and recrystallized from methanol-water. Yield, 9.0 g(93.7%) of 50/50 enantiomeric mixture. TLC (Hexane/ethyl acetate, 5/5):one spot, Rf=0.72. It was about 99% pure by HPLC (peak area percent)having a retention time of 19.85 min. It had important IR bands at 3342,2954, 1736, 1700, 1601, 1535, 1225, 1061 and 744 cm⁼¹. Elementalanalysis for C₂₁ H₂₆ N₄ O₃ (M.W. 382.5): Calcd. C, 65.95; H, 6.85; N,14.65. Found: C, 65.47; H, 6.72; N, 14.46. FD-MS: m/e 382 (M⁺). It hadNMR peaks in (CDCl₃) at δ 11.40 (s, 1H, phenolic OH), 8.3 (d, 1H,arom.), 7.9 (2 doublets, 2H, arom), 7.48 (2 doublets, 2H, arom), 7.24(s, 1H, arom.), 7.17 (2 doublets, 1H, arom.), 6.72 (s, 1H, NH), 4.1 (2doublets, 2H, OCH₂), 1.62 (m, 1H, aliphatic methine), 1.5-1.21 (m, 8H,4×CH₂ 's), and 0.95 (2 merging triplets, 6H, 2×CH₃ 's). Its UV-VIS(MeOH) showed a λ_(max) 343 nm and an ε_(max) 2.71×10⁴. M.P. 77°-78° C.

EXAMPLE 2 Inventive Compound No. VI ##STR17##

This compound was made the same way as (V), but starting with2-(2-hydroxy-4-ethylaminophenyl) benzotriazole. This was obtained as aliquid compound, 50/50 enantiomeric mixture. It was about 95% pure byHPLC (peak area percent) having a retention time of 25.23 min. Elementalanalysis for C₂₃ H₃₀ N₄ O₃ (M.W. 410.5): Calcd. C, 67.29; H, 7.37; N,13.65. Found: C, 67.15; H, 7.40; N, 13.76. FD-MS: m/e 410 (M⁺). It hadNMR peaks in (CDCl₃) at δ 11.40 (s, 1H, phenolic OH), 8.38 (d, 1H,arom.), 7.93 (2 doublets, 2H, arom), 7.5 (2 doublets, 2H, arom), 7.08(s, 1H, arom.), 6.92 (d, 1H, arom.), 4.02 (d, 2H, OCH₂), 3.78 (q, 2H,methylene of the N-ethyl group), 1.55 (m, 1 H, aliphatic methine), 1.23(m, 11H, 4×CH₂ 's and methyl of the N-ethyl group), and 0.87 (2 mergingtriplets, 6H, 2×CH₃ 's). Its UV-VIS (MeOH) showed a λ_(max) 334 nm andan ε_(max) 2.28×10⁴.

For making this compound 2-(2-hydroxy-4'-aminoethylphenyl)benzotriazolewas required. This was synthesized by reduction of the correspondingacetamido-substituted compound with alane in about 90% yield by similarprocedure known in the art (see, for example, Lal C. Vishwakarma et al,Heterocycles, 19, 1453 (1982)).

As already mentioned, the UV-VIS data of (VI) indicates a hypsochromicshift in its λ_(max) as well as lower molar extinction coefficient. Thismay be corrected by introducing a Cl-- or a F-- substituent at5-position in the benzo ring and substituting the ethyl group of R₄ withelectron-withdrawing groups such as trifluormethyl or any perfluoroalkylgroup.

EXAMPLE 3 Comparative Compound No. VII ##STR18##

This compound was made the same way as (V), but condensing withn-octyloxycarbonyl chloride in 94% yield. This was obtained as off-whitesolid. M.P. 131°-132° C. It was about 100% pure by HPLC (peak areapercent) having a retention time of 27.76 min. Elemental analysis forC₂₁ H₂₆ N₄ O₃ (M.W. 382.5): Calcd. C, 65.95; H, 6.85; N, 14.65. Found:C, 67.71; H, 6.90; N, 14.65. It had NMR peaks in (CDCl₃) at δ 11.3 (s,1H, phenolic OH), 8.3 (d, 1H, arom.), 7.84 (2 doublets, 2H, arom), 7.42(2 doublets, 2H, arom), 7.21 (s, 1H, arom.), 7.10 (2 doublets, 1H,arom.), 6.7 (s, 1H, NH), 4.18 (t, 2H, OCH₂), 1.62 (m, 2H, methylene),1.30 (m, 10H, 5×CH₂ 's ), and 0.88 (t, 3H, CH₃). Its UV-VIS (MeOH)showed a λ_(max) 343.8 nm and an ε_(max) 2.70×10⁴.

This comparative compound is lacking a racemic carbon center, otherwiseit is an exact match with the inventive compound (V) having the sametotal number of atoms the same in both.

EXAMPLE 4 Comparative Compound No. VIII ##STR19##

This compound was made the same way as (V), but condensing withiso-butyryloxycarbonyl chloride in 90% yield. This was obtained asoff-white solid. M.P. 154°-155° C. Elemental analysis for C₁₇ H₁₈ N₄ O₃(M.W. 326.4): Calcd. C, 62.57; H, 5.56; N, 17.17. Found: C, 62.49; H,5.64; N, 17.03. It had NMR peaks in (CDCl₃) at δ 11.35 (s, 1H, phenolicOH ), 8.3 (d, 1H, arom.), 7.9 (2 doublets, 2H, arom), 7.42 (2 doublets,2H, arom), 7.22 (s, 1H, arom.), 7.10 (d, 1H, arom.), 6.78 (s, 1H, NH),3.95 (d, 2H, OCH₂), 2.0 (m, 1H, methine), and 0.9 (d, 6H, isopropylgroup). Its UV-VIS (MeOH) showed a λ_(max) 343 nm and an ε_(max)2.69×10.sup. 4.

This compound was made as a comparative example with a branched chainbut lacking a racemic carbon center. As shown in Table 1, branching ofthe chain only does not provide a compound with the same performance asan inventive compound having a racemic center in the 4'-Carbamato, suchas compound (V).

EXAMPLE 5 Comparative Compound No. IX ##STR20##

This compound was made the same way as (V), but condensing2-(2-hydroxyphenyl)-5-amino benzotriazole with ethoxycarbonyl chloride.This was obtained as off-white solid in 87% yield. M.P. 192°-193° C.Elemental analysis for C₁₅ H₁₄ N₄ O₃ (M.W. 298.3): Calcd. C, 60.40; H,4.73; N, 18.78. Found: C, 60.25; H, 4.87; N, 18.66. It had NMR peaks in(CDCl₃ ) at δ 11.25 (s, 1H, phenolic OH ), 8.35 (2 doublets, 1H, arom.),8.13 (s, 1H, arom), 7.83 (d, 1H, arom), 7.3 (m, 2H, arom.), 7.2 (d, 1H,arom.), 7.02 (t, 1H, arom.), 6.8 (s, 1H, NH), 4.28 (q, 2H, OCH₂), and1.35 (t, 3H, CH₃). Its UV-VIS (MeOH) showed a λ_(max) 347 nm and anε_(max) 2.15×10⁴.

EXAMPLE 6 Comparative Compound No. X ##STR21##

This compound was made the same way as (V), but condensing2-(2-hydroxyphenyl)-5-amino benzotriazole with 2-ethylhexyloxycarbonylchloride. This was obtained as off-white solid in 90% yield. M.P.103°-105° C. Elemental analysis for C₂₁ H₂₆ N₄ O₃ (M.W. 382.5): Calcd.C, 65.95; H, 6.85; N, 14.65. Found: C, 65.76; H, 6.80; N, 14.53. It hadNMR peaks in (CDCl₃) at δ 11.25 (s, 1H, phenolic OH), 8.35 (d, 1H,arom.), 8.15 (s, 1H, arom), 7.82 (d, 1H, arom), 7.3 (m, 2H, arom.), 7.2(d, 1H, arom.), 7.0 (t, 1H, arom.), 6.83 (s, 1H, NH), 4.1 (2 doublets,2H, OCH₂), 1.62 (m, 1H, methine), 1.38 (m, 2H, CH₂), 1.3 (broad singlet,6H, 3×CH₂ 's), and 0.9 (t, 6H, 2×CH₃ 's). Its UV-VIS (MeOH) showed aλ_(max) 347 nm and an ε_(max) 2.26×10⁴.

EXAMPLE 7 Comparative Compound No. XI ##STR22##

2-(2-Hydroxy-4-amino phenyl)benzotriazole (20 g, 0.0885 mole), glacialacetic acid (250 mL) and p-toluenesulfonic acid monohydrate (known asPTS, 0.8 g, a catalytic amount) were refluxed on a heating mantle for 16hours. This was then cooled to room temperature and poured into 1 literof ice-cold water. Insoluble off-white product was filtered on asintered glass funnel, and washed with methanol/water (1/1, 2×50 mL),and was air-dried. Its TLC (Hexane/ethyl acetate; 6/4) had an Rf 0.49.Yield, 23.0 g (98%). M.P. 220°-221° C. It had NMR peaks in (CDCl₃) at δ11.7 (s, 1H, phenolic OH), 8.3 (d, 1H, arom.), 8.02 (2 doublets, 2H,arom), 7.82 (s, 1H, arom), 7.6 (2 doublets, 2H, aromo), 7.38 (d, 1H,arom.), and 2.22 (s, 3H, CH₃). Its UV-VIS (MeOH) showed a λ_(max) 344 nmand an ε_(max) 2.65×10⁴.

EXAMPLE 8 Comparative Compound No. XII ##STR23##

This compound was prepared in the same way as the Inventive Compound(V). Thus 2-(2-hydroxy-4-aminophenyl)benzotriazole was condensed with2-ethylhexanoyl chloride. It was obtained as a white solid. M.P.169°-170° C. Elemental analysis for C₂₀ H₂₄ N₄ O₂ (M.W. 352.4): Calcd.C, 68.16; H, 6.86; N, 15.90. Found: C, 68.10; H, 6.90; N, 15.78. It hadNMR peaks in (CDCl₃) at δ 11.4 (s, 1H, phenolic OH), 8.3 (d, 1H, arom.),7.92 (2 doublets, 2H, arom), 7.42 (m, 3H containing the NH proton), 7.25(d, 1H, arom.), 2.1 (m, 1H, methine), 1.7 (m, 2H, CH₂), 1.55 (m, 2H,CH₂), 1.3 (tall doublet, 4H, 2×CH₂ 's), 0.98 (t, 3H, CH₃), and 0.9 (t,3H, CH₃). Its UV-VIS (MeOH) showed a λ_(max) 344 nm and an ε_(max)2.76×10⁴.

EXAMPLE 9 Comparative Compound No. XIII ##STR24##

This compound was made the same way as (XI). M.P. 215°-216° C. Elementalanalysis for C₁₄ H₁₂ N₄ O₂ (M.W. 268.3): Calcd. C, 62.68; H, 4.51; N,20.88. Found: C, 62.44; H, 4.63; N, 20.57. It had NMR peaks in (CDCl₃)at δ 11.3 (s, 1H, phenolic OH), 9.9 (s, 1H, CONH), 9.1 (s, 1H, arom),8.9 (d, 1H, arom.), 8.4 (d, 1H, arom.), 8.12 (m, 1H, arom), 7.92 (t, 1H,arom.), 7.78 (d, 1H, arom), 7.65 (t, 1H, arom.), and 2.8 (s, 3H, CH₃).Its UV-VIS (MeOH) showed a λ_(max) 346 nm and an ε_(max) 2.27×10⁴.

EXAMPLE 10 Comparative Compound No. XIV ##STR25##

This compound was made the same way as (XII) in 95% yield. It contains aracemic carbon center in the amide chain. M.P. 199°-200° C. Elementalanalysis for C₂₀ H₂₄ N₄ O₂ (M.W. 352.4): Calcd. C, 68.16; H, 6.86; N,15.90. Found: C, 68.18; H, 6.86; N, 15.71. It had NMR peaks in (CDCl₃)at δ 11.3 (s, 1H, phenolic OH), 8.4 (s, 1H, CONH), 8.32 (d, 1H, arom),7.85 (d, 1H, arom.), 7.48 (s, 1H, arom.), 7.4 (d, 1H, arom), 7.32 (t,1H, arom.), 7.2 (d, 1H, arom), 7.0 (t, 1H, arom.), 2.18 (m, 1H,methine), 1.72 (m, 2H, CH₂), 1.58 (m, 2H, CH₂), 1.3 (doublet, 4H, 2×CH₂'s), 0.96 (t, 3H, CH₃), and 0.9 (t, 3H, CH₃). Its UV-VIS (MeOH) showed aλ_(max) 346 nm and an ε_(max) 2.31×10⁴.

EXAMPLE 11 Comparative Compound No. XV ##STR26##

This compound was made the same way as (XII) in 95% yield. It containsnon-racemic carbon center in the amide chain (a normal straight chainversion with the same number of carbon atoms). M.P. 169°-170° C.Elemental analysis for C₂₀ H₂₄ N₄ O₂ (M.W. 352.4): Calcd. C, 68.16; H,6.86; N, 15.90. Found: C, 68.44; H, 669; N, 15.43. It had NMR peaks in(CDCl₃) at δ 11.5 (s, 1H, phenolic OH), 8.39 (s, 1H, CONH), 8.30 (d, 1H,arom), 7.83 (d, 1H, arom.), 7.3 (m, 3H, arom.), 7.18 (d, 1H, arom), 7.02(t, 1H, arom.), 2.4 (t, 2H, CH₂), 1.75 (m, 2H, CH₂), 1.3 (broad doublet,8H, 4×CH₂ 's), and 0.9 (t, 3H, CH₃ ). Its UV-VIS (MeOH) showed a λ_(max)346 nm and an ε_(max) 2.28×10⁴.

PROPERTIES OF THE UV ABSORBERS OF THE PRESENT INVENTION

Physical properties, including optical absorption profiles were measuredfor various of the compounds of the present invention, as well ascomparative compounds, as shown in Table 1 below. In Table 1, λ_(max) isthe wavelength of maximum absorption (measured in MeOH as indicated inthe Table), ε_(max) is the extinction coefficient, and the halfbandwidth is the width of the absorption peak centered about λ_(max) asmeasured at one-half the maximum absorption λ_(max). All of theforegoing were measured in methanol.

                                      TABLE 1                                     __________________________________________________________________________                          λ.sub.max (nm)                                                               ε.sub.max                                                                  Half Band-                                                                          Melting                                Comp. No. Example No.                                                                          % Yield                                                                            (in MeOH)                                                                           (× 10.sup.4)                                                                 width (nm)                                                                          Point (°C.)                     __________________________________________________________________________    Inventive, V                                                                            1      93   343   2.71 58    77-78                                  Inventive, VI                                                                           2      85   334   2.28 57    Liquid                                 Comparative, VII                                                                        3      94   344   2.70 59    131-132                                Comparative, VIII                                                                       4      90   343   2.69 57    154-155                                Comparative, IX                                                                         5      87   347   2.15 55    192-193                                Comparative, X                                                                          6      90   347   2.26 55    103-105                                Comparative, XI                                                                         7      98   344   2.65 59    220-221                                Comparative, XII                                                                        8      86   344   2.76 59    169-170                                Comparative, XIII                                                                       9      88   346   2.27 56    215-216                                Comparative, XIV                                                                        10     95   346   2.31 55    199-200                                Comparative, XIV                                                                        11     95   346   2.28 55    169-170                                __________________________________________________________________________

Table 1 illustrates the higher melting character of the comparativeexamples related to prior arts. As a result, they are prone tocrystallize out in the dispersion and/or coating even if they haveracemic chains particularly in primary carboxamido substitutedcompounds.

PHOTOGRAPHIC EVALUATION

1.45 g of UV absorber was dissolved at elevated temperature (50°-70° C.)in 480 mg of 1,4-cyclohexylenedimethylene bis (2-ethylhexanoate) and, ifUV absorber was a solid at room temperature, an additional 4.35 g ofethyl acetate was used. This oil phase was added with high shearstirring to a 70° C. aqueous gelatin solution (containing per liter 40.1g of gelatin and 31.0 mL of 10% aqueous Alkanol--XC) and passed fivetimes through a colloid mill for adequate particle size reduction. Thedispersion is inspected microscopically for general particle size andcrystallinity, and coated @ 1.16×10⁻⁴ moles/ft² on an acetate base in atwo layer SOC-type format, allowed to dry and the coating is alsoinspected microscopically for crystallinity (See Table 2). Fresh coatedspectral absorption data are recorded using a Perkin-Elmer Lambda 4CHigh Performance UV-VIS Spectrophotometer, and coated samples are HID(50 Klux Daylight; 315-700 nm) and HIS (50 Klux Sunshine; 280-700 nm)tested and compared to fresh data in order to obtain UV absorberintrinsic light stability information. (For HID and HIS explanation, seeLewis R. Koller, Ultraviolet Radiation, John Wiley & Sons, Inc., N.Y.,N.Y., 1965).

Absorption spectra for various of the compounds were obtained insolution and in coating as described below and are shown in FIGS. 1& 2.In particular, FIG. 1 shows the normalized absorption spectra inmethanolic solution for a mixture of comparative control compounds II-Aand II-B (solid line), as well as for the inventive compound V (dottedline). FIG. 2 shows the absorption spectra in coating for inventivecompound and the control compounds in total transmission mode of thespectrophotometer. Note from FIG. 1 that the inventive UV absorbingcompound has about the same absorbance as a commonly used mixture ofcontrol UV absorbing compounds II-A/II-B in the important region ofabout 330-370 nm. However, the inventive compound has steeper slope atits longer wavelengths of absorption (that is, near 380 nm) andparticularly drop to a lower absorption at their longest wavelength ofthe absorption, than does the mixture of II-A/II-B. Note from FIG. 2that inventive UV absorbing compound exhibits, in addition to a steeperslope, a far higher extinction coefficient than comparative controlcompounds II-A/II-B as measured from fresh coating of their respectivedispersions.

Microscopic observations for crystallinity in experimental UV absorberdispersions and coatings of these materials and their absorption spectrawere performed as described here. Microscopy is undertaken in thepreparation of dispersions of experimental materials in order to providean initial indication of physical properties such as general particlesize and stability (that is, is the particular material susceptible tocrystallize). The microscopic particle size characterizations areperformed using oil immersion optics ˜1000×microscopy, and˜200×cross-polarized microscopy is used for crystal characterization.Microscopic evaluation of the coatings is also undertaken because anacceptable non-crystalline dispersion may recrystallize in the coatedformat. Assuming there are no re-crystallization problems, duplicatesamples are spectrophotometrically measured using a Perkin-Elmer HighPerformance Lambda 4C spectrometer. These samples are then submitted fortwo Week HID and HIS light stability testing, and the post-testingspectra is measured and compared to the fresh measurements in order todetermine intrinsic light stability of the UV absorber. Since theexperimental dispersion formulation used for these experiments is commonand only optimized from the standpoint of low melting solids and itsbeneficial effect on dispersion crystallinity, coated spectroscopy dataare obtained primarily using the total transmission mode of operationwhere an integrating sphere is used in the spectrophotometer. This hasthe effect of diminishing light scattering effects due to particle size,so misleading extinction differences caused by light scattering in thespecular mode can be overlooked.

A microscopic check for crystal formation from the above procedure,yielded the results in Table 2 below:

                  TABLE 2                                                         ______________________________________                                        Tendency to Form Undesirable Crystals                                         Compound No.                                                                              Example No.                                                                              Dispersion Coating                                     ______________________________________                                        Inventive, V                                                                              1          It did not It did not                                                         crystallize                                                                              crystallize                                 Inventive, VI                                                                             2          A liquid   A liquid                                    Comparative, VII                                                                          3          Crystallized                                                                             Crystallized                                Comparative, VIII                                                                         4          Crystallized                                                                             Crystallized                                Comparative, IX                                                                           5          Crystallized                                                                             Crystallized                                Comparative, X                                                                            6          It did not Crystallized                                                       crystallize                                            Comparative, XI                                                                           7          Crystallized                                                                             Crystallized                                Comparative, XII                                                                          8          Crystallized                                                                             Crystallized                                Comparative, XIII                                                                         9          Crystallized                                                                             Crystallized                                Comparative, XIV                                                                          10         Crystallized                                                                             Crystallized                                Comparative, XV                                                                           11         Crystallized                                                                             Crystallized                                ______________________________________                                    

Table 2 illustrates how UV absorbing compound V of the present inventiondid not form any detectable crystals either in dispersion or in coating.On the other hand, the compound VII being an exact match in terms ofnumber of atoms and position of carbamato group attachment in thehydroxyphenyl ring, but lacking a racemic carbon center did not evendissolve in the dispersion. As mentioned earlier, the presence of aracemic carbon center in comparative compound X (another exact match butwith different point of attachment) did influence it to go in thedispersion. However, this compound crystallized out in the coating. Thisobservation further emphasizes the importance of a combination of acarbamate group, alkyl chains in the carbamate group possessing racemiccarbon center(s), and most importantly the point of attachment of thecarbamato group in the benzotriazole UV chromophore which is 4'- in thehydroxyphenyl ring.

Intrinsic light stability data for inventive UV absorber compound V aresummarized in Table 3. A combination of the compounds II-A & II-B hasbeen used as a Control in each coating set. The optical density loss,relative to the control coatings, was measured at 350 nm from coatingspectral data.

                  TABLE 3                                                         ______________________________________                                        Sample              2 Week   2 Week                                           Number              HID      HIS                                              ______________________________________                                        Control Compounds II-A/II-B                                                                       -5.21    -6.60                                            Inventive Compound V                                                                              -2.97    -6.77                                            ______________________________________                                    

The two week intrinsic light stability data from Table 3 suggest thatthe inventive compound V is at least equal to or better than the controlcompounds II-A/II-B.

It will be seen from the data of Tables 1 and 2 above, that inparticular the comparative compounds (IX) and (X) (which contain thecarbamato group at a location such as at 5-position in the benzo ringwith or without a racemic chain) exhibit a hue which is not asacceptable as the Inventive Compound (V), have lower molar extinctioncoefficients, and are higher melting compounds and crystallize out inthe dispersion as well as in the coating.

Additionally, as shown in Tables 1 and 2, carboxamido substitutedbenzotriazole examples (Compound Numbers XI through XV) regardless ofthe characteristics of the attached carbon chains had somewhat deeperhue, lower extinction coefficient and crystallized out in dispersion orin coating. This observation further illustrates that the benzotriazolecompounds, which could be used in a conventional dispersion formatsatisfying the criteria for color photographic paper, exhibit superiorperformance when they fall under the formula (I) of the presentinvention (that is, they contain a racemic carbamato substitutent at4'-position in the hydroxyphenyl ring).

The present invention also specifically contemplates multilayerphotographic elements as described in Research Disclosure, February1995, Item 37038 (pages 79-115). Particularly contemplated is the use ofany of the enantiomeric mixtures of formula (I) (particularly a 50/50mixture of the two enantiomers) in such elements. Particularly, a 50/50enantiomeric mixture of any one of the compounds in Tables A and B orCompounds V and VI, may be used as the UV absorbing compound in anovercoat of each of the photographic elements described in detail inSections XVII through XXII of that Research Disclosure.

The preceding examples are set forth to illustrate specific embodimentsof this invention and are not intended to limit the scope of thecompositions or materials of the invention. It will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:
 1. A photographic element comprising at least one lightsensitive layer and an ultraviolet absorbing compound of the followingstructure: ##STR27## wherein: R₄ is H or an alkyl group, and the benzoor phenyl ring shown may be further substituted or unsubstituted;X is--C(O)O-- wherein the carbonyl carbon is bonded to the N of NR₄, or X is--SO₂ --; L is a bivalent linking group; p is 0 or 1; A* is an alkylgroup having an asymmetric carbon or silicon atom, and; wherein theultraviolet absorbing compound of formula (I) is a mixture of twoenantiomers about the asymmetric carbon or silicon of A*.
 2. Aphotographic element according to claim 1 wherein p is 1 and L is analkylene group having a chain of 1 to 20 atoms in length, with orwithout intervening oxygen, sulfur or nitrogen atoms.
 3. A photographicelement according to claim 1 wherein the ultraviolet absorbing compoundis a 60/40 to 40/60 mixture of two enantiomers.
 4. A photographicelement according to claim 1, the element additionally comprising anon-light sensitive layer, wherein the ultraviolet absorbing compound islocated in the non-light sensitive layer.
 5. A photographic elementaccording to claim 4 wherein the non-light sensitive layer containingthe ultraviolet absorbing compound is located above all of the lightsensitive layers.
 6. A photographic element according to claim 1,additionally comprising a reflective support and at least one silverhalide emulsion layer, and wherein the ultraviolet absorbing compound islocated in the silver halide emulsion layer or in a layer positionedfurther from the support than the silver halide emulsion layer.
 7. Aphotographic element according to claim 6 additionally comprising afluorescent brightener.
 8. A photographic element according to claim 6wherein the fluorescent brightener absorbs ultraviolet in the 350-410 nmrange in order to fluoresce in the range of 400-500 nm.
 9. Aphotographic element according to claim 1 wherein the ultravioletabsorbing compound is present in an amount of between 0.2 g/m² to 10g/m².
 10. A photographic element comprising at least one light sensitivelayer and an ultraviolet absorbing compound of the following structure:##STR28## wherein: R₁, R₂ or R₃ independently represent alkyl group,alkoxy group, aryl group, heteroaryl group, or aryloxy group, and thealkyl or alkoxy may contain from 1 to 5 intervening oxygen, sulfur ornitrogen atoms, or any of R₁, R₂ or R₃ is H, cyano or a halogen atom, orboth R₁ and R₂ together form an aromatic group or hetero aromatic group,or R₃ can additionally be H or 6'-hydroxy;R₄ is H or an alkyl group; Xis --C(O)O-- wherein the carbonyl carbon is bonded to the N of NR₄, or Xis --SO₂ --; L is a bivalent linking group; p is 0 or 1; and R₅, R₆ andR₇ are, independently: H; halogen; cyano; an alkyl group or alkoxygroup; thioalkyl group; alkylamino or arylamino group; an aryl group oraryloxy group; or a heteroaryl group; provided that R₅, R₆, and R₇ areselected such that the carbon atom to which they are attached isasymmetric; the ultraviolet absorbing compound being a 60/40 to 40/60mixture of two enantiomers about the asymmetric carbon atom joining(L)_(p), R₅, R₆ and R₇.
 11. A photographic element according to claim 10wherein R₅, R₆ and R₇ are each a 1 to 20 carbon atom alkyl group, or H.12. A photographic element according to claim 11 wherein each of R₁, R₂and R₃, is an alkyl group, alkoxy group, H or halogen.
 13. Aphotographic element according to claim 10 wherein the ultravioletabsorbing compound of formula (I) is a 50/50 mixture of two enantiomers.14. A photographic element according to claim 1, the elementadditionally comprising a non-light sensitive layer, wherein theultraviolet absorbing compound is of the following formula: ##STR29##wherein: R₁, R₂ and R₃ independently represent alkyl group, alkoxygroup, aryl group, heteroaryl group, or aryloxy group, and the alkyl oralkoxy may contain from 1 to 5 intervening oxygen, sulfur or nitrogenatoms, or may contain double bonds, or any of R₁, R₂ or R₃ is H, cyanoor a halogen atom, or both R₁ and R₂ together form an aromatic group orhetero aromatic group;R₄ is H or an alkyl group; L is a bivalent linkinggroup; p is 0 or 1; and R₅, R₆ and R₇ are, independently: H; halogen;cyano; an alkyl group or alkoxy group; thioalkyl group; alkylamino orarylamino group; an aryl group or aryloxy group; or a heteroaryl group;provided that R₅, R₆, and R₇ are selected such that the carbon atom towhich they are attached is asymmetric; the ultraviolet absorbingcompound being a 60/40 to 40/60 mixture of two enantiomers about theasymmetric carbon atom joining (L)_(p), R₅, R₆ and R₇.
 15. Aphotographic element according to claim 14, wherein the ultravioletabsorbing compound is of the formula: ##STR30## wherein R₄, R₅, R₆, R₇,L and p are as defined in claim
 14. 16. A photographic element accordingto claim 15 wherein L is a 1 to 10 carbon atom alkylene group.
 17. Aphotographic element according to claim 16 wherein p is
 1. 18. Aphotographic element according to claim 17 wherein L is a methylenegroup.
 19. A photographic element according to claim 14 wherein R₄ is H.20. A photographic element according to claim 16 wherein R₄ is H.
 21. Aphotographic element according to claim 14, wherein the ultravioletabsorbing compound is located in the non-light sensitive layer.
 22. Aphotographic element according to claim 14 wherein the non-lightsensitive layer containing the ultraviolet absorbing compound is locatedabove all of the light sensitive layers.
 23. A photographic elementaccording to claim 14, additionally comprising a reflective support andat least one silver halide emulsion layer, and wherein the ultravioletabsorbing compound is located in the silver halide emulsion layer or ina layer positioned further from the support than the silver halideemulsion layer.
 24. A photographic element according to claim 1 whereinwhen R₄ is an alkyl group, it is an electron withdrawing alkyl group.